Distillation process for separating products of chloroform fluorination



Get-5, 1948. A., F. BENNINGY 2,450,414

DISTILLATION PROCESS FOR SEPARATING PRODUCTS OF CHLOROFORM FLUORINATION Filed NOV. 14, 1946 JNVENTOR. Anthony F. Banning ATTORNEY Patented c s, 1948 2,450,414

DISTILLATION PROCESS FOR SEPARATING gIItSgIJUCTS OF CHLOROFORM FLUORINA- Anthony F. Benning, Woodstown, N. J., assignor to Kinetic Chemicals, Inc, Wilmington, Del., a corporatlon of Delaware Application November 14, 1946, Serial No. 709,879

6 Claims. (Cl. 202-51) ture obtained in the fluorination of chloroform.

In the fluorination of chloroform in the presence of an antimony catalyst, there is produced a reaction mixture comprising mainly HCl. CHClF'a and CHClzF with small proportions of HF and usually small amounts of unreacted CHCb and less than 0.5 mol per cent of CHFa. The separation of the valuable components of such mixture has been attended with considerable difllculty. The usual procedure has been to wash the reaction mixture with water to remove the acidic components, drying and condensing the 2 temperatures of from about -63 C. to about 20 C. adjusted to the pressures to distill oil substantially pure anhydrous 1101 while retaining the rest of the mixture in the still. The mixture, remaining in the still, may then be subjected to a further anhydrous fractional distillation under pressures of from about '0 to about 100 pounds per square inch gauge and at temperatures of from about 43 C. to about 20 C., adjusted to the pressures to distill off CI-IClFz and part of the HF from the rest of the mixture. The mixture of CHClF2 and HF is then passed to a scrubber where it is washed with a small amount of water to remove the HF. The remainder of the reaction washed products and then subjecting to fracmixture may be recycled for further reaction but tional distillation to remove the chlorodifluoropreferably is caused to settle untilit forms a methane. During the reaction, only about 50% layer of organic products, containing dissolved of the CHCla is converted to CHCIF; so that the HE, and a layer of substantially anhydrous HF, reaction mixture contains about 56 mol per cent containing dissolved CHClzF, which layers are of HCl, about 18 mol per cent of CHClFz, about 19 20 separated. The separated organic products may mol per cent of CHClzF and smaller amounts of then be subjected to a further anhydrous distilla- HF, CHF: and CHC13. This requires the use of tion to separate the CHClzF and dissolved HF large size equipment to wash, dry and condense from any unreacted CHClx. The CH0]: and the the large amounts of CHC12F and other organic separated HF layer may then be recycled for furproducts in the reaction mixture. Also, very subther reaction.

stan'tial amounts of valuable organic products are I have found that, by such process, I am able to lost by solution in the wash water. This proceeifectively separate the reaction mixture into its dure further involves the loss of valuable HCl in valuable components in an easy and economical the form of an aqueous solution contaminated manner and to .largely overcome the objections with HF and organic products. Furthermore, 0 of the method previously employed. Only relawhen it was attempted to frac'tionally distill the reaction mixture, it was found that the distillatlon characteristics of the various components varied so much and were so inconsistent that, prior to my invention, it was not possible to carry out an eflicient and economical separation.

It is an object of the present invention to provide a process for recovering the valuable components from areaction mixture obtained by I smallproportions of HF, to anhydrous fractional distillation under pressures of from about 40 to about 200 pounds per square inch gauge and at tively small amounts of material are subjected to the washing, drying and condensing steps, whereby large economies are effected in the process and in the apparatus employed. Furthermore, the HCl is recovered in a commercially valuable and usable form. There is also a substantially complete recovery of organic reactants since none is lost by solution in the scrubbing water. Furthermore, there is a substantial saving of HF by recycling the HF layer, since the HF therein is not lost by solution in the scrubbing water. It will thus be apparent that by my process, I am able to effectively recover the valuable components of the reaction mixture in a simple and easy manner and to efiect large economies in the Process and in the apparatus.

In order to more clearly illustrate my invention and the best modes of carrying the same into efiect, my invention will be described in more detail with reference to the accompanying drawing which illustrates one form of apparatus, shown somewhat digrammatically, which may be employed for carryin out my invention.

The apparatus shown in Fig. 1 of the drawings comprises a reaction vessel ID, a reflux column I2,

3 a dephlegmator H, a brine cooled catch tank It, a reflux connected in series by suitable conduits. A still pot i8 is connected to the bottom of the reflux column 20. There is also provided a reflux column 26, adephlegmator 28 and a still pot 24 connected by suitable conduits. A conduit leads from the still pot l8 to the reflux column 28. The dephlegmator 28 is connected to a scrubber, not shown. The still pot is connected to the settling tank 30 through a suitable conduit. The still pct 24 may-be provided with a conduit for withdrawing still residues therefrom and recycling them to the reaction vessel ID. The settling tank 30 is provided with a member 32 for indicating the level of interface between the two layers. A conduit is provided for withdrawing the HF layer from the settling tank 30 and recycling it to the reaction vessel l0. Another conduit is provided for drawing off the mixture of CHChF and CH]: from the tank 30 and conducting it to a reflux column 36 provided with a dephlegmat'or 40 and a still pct 38. A conduit is provided for withdraw-ingCHCls from the pot 38 and recycling it to the reaetionves'sel III.

In operation, CHCla and HF are passed to the reaction vessel l0, containing a fluorination catalyst, wherein the CHCla is fiuorinated to produce CHCIF: and other products. A suitable catalyst may be prepared by placing a mixture of about 400 parts 01'. SbCls and about 40 parts of SbCl: in the reaction vessel and then passing HF through the mixture until the fluorine content therein is about 1% to about 7%. The reaction mixture is passed from the reaction vessel through the reflux column I: and dephlegmator ll, operated to retain CHCla and CHChF for maximum conversion to CHClFa. The reaction products then pass to the catch tank l6 wherein they are freed from entrained catalyst such as antimony salts. The

gaseous reaction mixture is. compressed into the middle of the reflux column 20, employing a pump or compressor where necessary. The mixture, entering the refluxcolumn 20, is either gaseous or partially liquid and partially gaseous, depending upon the temperature and pressure.

The'reflux column 20 and the dephlegmator 22 are operated at temperatures, corresponding to the pressure employed. to distill ofi substantially pure anhydrous HCl together with any CHFa which may be present which are taken oil? at the top. The CHF: will ordinarily be less than 0.5 mol per cent of the H01. With pressures of about 100 pounds per square inch gauge, the dephlegmator temperature will be from about -40 C. to about 50 C. I have found these last temperatures and pressures to be the most practical, but higher or lower pressures may be used with the temperatures adiusted accordingly. The still pot l8 will be heatedto give a pot temperature of about 15 C. to about 30 0.. depending upon the proportion 01' CHChF in the mixture, the higher temperatures being employed with higher proportions of CHClaF.

The other components of the reaction mixture will pass to and be collected in the still pot l8. The residue in the still pot will be forced, by autogenous pressure, into the reflux column 26. There will be a slight pressure drop so that the reflux column 26 will normally operate at slightly lower pressures than the reflux column 20, e. g., at from about 35 to about '70 pounds per square inch gauge. Ii desired, a compressor or other means can be included toincrease the pressure in the reflux column 26, but this will generally column 20 and a dephlegmator 22, all

be unnecessary. Preferably, the pressure in the reflux column 28 and the dephlegmator 2! will be about 50 pounds per square inch gauge. At these pressures, the temperature in the dephlegmator will be about -5 C. to about 0 C. By this means, there is obtained a substantially complete separation of the CHCIF: and about 60% of the HF from the rest of the reaction mixture. The distillate is an azeotrope and contains from about 1% to about 2.2% by weight of HF. The distillate mixture of CHClFa and HF will be passed directly to a scrubber wherein the HF canbe removed from the; CHClF: by washing with a small amount of wa er.

The mixture in the still pct 24 may b recycled to the reaction vessel 10 but, preferably, will be passed to the settling tank 30. Upon settling. there is formed an HF layer and an organic layer. The HF'layer consists of substantially-anhydrous HF and a minor proportion of CHClrF dissolved therein. The amount of CHClzF dissolved in the HF will depend on the temperature, varying from about 14% by weight at 30 C. to about 26% square inch gauge.

by weight at +20 C. The organic layer consists essentially of CHClaF and CHCl, having dissolved therein a small proportion of HF. The amount of HF dissolved in the organic layer will also depend on the temperature, the solubility of HF in CHClzF varying from about 0.6% by weight at 30 C. to about 2.2% by weight at +20 C. In practice, the amount of HF dissolved in the organic layer will usually be less than this, depending on the amount of CHCla present.

The HF layer will be withdrawn from tank 30 and passed to the reaction vessel ID or to storage. The lower organic layer in the tank 30, comprising CHClaF, unreacted CHCls, and dissolved HF.

may be returned to the reaction vessel ill for fur ther fluorination. Preferably, however, the organic layer will be withdrawn from tank 30 and passed to reflux column 36. The reflux column 36 and dephlegmator 40 will'be operated at pressures of from about 30 to about 65 pounds per The temperature of the vapors in the dephlegmator 40 will be from about 41 C. to about 63 C., adjusted to the pressures to distill-oi! CHChF and HF and to retain CHCls, which is passed to the still not )8 and then recycled to the reaction vessel ID for fluorination.

The residues in the still pots I8, 24 and 38 will preferably be allowed to build up until the pots are about half full and the residues will be drawn on therefrom as necessary to maintain the pots about half full. If all of the still residue were removed from each pot, thestills would tend to operate erratically. By maintaining each still pot about half full of residue, smoother and bette still performance is obtained.

In order to illustrate my invention, the following example is given:

Example A mixture consisting essentially of 400 parts of Shela, 20 parts of SbCla, and 500 parts of CHCla is placed in reactor I0. While the mixture is maintained at about 70:t5 C., and p. s. i. g.. 50 parts of HF and parts of CHCla per hour are added simultaneously into the reactor. During the operation, the reflux temperature in the dephlegmator is not allowed to rise above 20 C. at 120 p. s. i. g. This pressure is substantially equal to the vapor pressure of CHClFz at the temperature 20 C. If the autoclave and column are operated at pressures greater than this, correspondingly higher dephlegmator temperatures can beimaintained.

The product gases from the top of the dephlegcolumn where it is continuously fractionated to remove the HCl and any CHF; from the other products. The dephlegmator of this HCl distillation unit is maintained under pressure-temperature conditions which will reflux anhydrous HCl and the small amount of CHFs produced. These conditions correspond closely to. 100 p. s. i. g. at the temperature of ---40 C. The EC] still pot is heated to give a pot temperature of about 25 C. The reaction products, remaining at the bottom of the HCl still, consist essentially of CHClzF, CHClFa, HF, and traces of chloroform. A standpipe in the pot connects it with the CHCIF: still column. The controls are so arranged that, when the HCl still-pt becomes half full, a valve in the line to the CHCiFz column is opened and the CHClF-z and other high boilers are forced, by the hereinbefore described, illustrates one type of appressure of the HCl still, into the CHClFz still which is operated at a lower pressure (50 p. s. i. g.). This valve'is throttled so as to maintain a steady flow into the CHClFa still. The CHClFz column is operated to maintain the temperature and pressure in the dephlegmator equivalent to the saturation values for CHClFz. In this case, this is a pressure of 50 p. s. i. g. at the dephlegmator temperature of to 0 C. From the CHClFz still dephlegmator, the desired fluorinated compound CHClFz and the HF which comes off with it are sent to the water scrubber, then through dryers and compressed. This material is of sufllcient purity to be of refrigerant grade. The CHClFz still pot is, similarly equipped with a standpipe, like that in the HCl still pot, for the removal of CHC12F, CHC]3, and HF collecting in the pot. From this pot, the mixture can be fed either into the catalyst pot or it can be passed into the brine-cooled organic-HF separator. In this separator, the HF layer is the top layer andthe organic layer can be drawn oil. the bottom and separated by distillation or fed directly back into the reactor.

The apparatus and the operation thereof, as

paratus for a continuous process. Other types of apparatus may be substituted therefor. Also, the process may be operated batch'wise in suitable apparatus therefor. Furthermore, pressures, higher and lower'than those disclosed, may be employed with suitable adjustment of the temperatures in accordance with the principles of my invention. Therefore, my invention is not The gases from the 6 from about 63 C. to about -20 0., adjusted to the pressures to distill oil! the HCl as substantially pure anhydrous hydrogen chloride, then subjecting the remaining mixture to a further anhydrous fractional distillation under pressures of from about 0 to about 100 pounds per square 'inch gauge and at temperatures of from about -43 C. to about 20 'C., adjusted to the pressures to distill off a mixture comprising substantially the monochlorodifluoromethane and part of the hydrogen fluoride, settling the undistilled mixture until it forms a layer of substantially anhydrous hydrogen fluoride containing a minor proportion of dissolved dichloromonofluoromethane and a layer comprising dichloromonofluoromethane, and separating the layers.

2. The process of separating valuable components from a. reaction mixture comprising HCl,

HF, CHC1F2 and CHClzF, of the character oi? that obtained by the reaction of HF on CHCla, which comprises the steps of subjecting the reaction mixture to anhydrous fractional distillation under pressures of about 100 pounds per square inch gauge and at about -50 C. to about C. to distill off the HCl as substantially pure anhydrous hydrogen chloride, then subjecting the remaining mixture to a further anhydrous fractional distillation under pressures of about pounds per square inch gauge and at about 5 C. to about 0 C. to distill off. a mixture comprising substantially the monochlorodifiuoromethane and-part of the hydrogen fluoride, settling the undistilled mixture until it forms a, layer to be limited to the specific embodiments disclosed, but I intend to cover my invention broadly as in the appended claims.

This is a continuation-in-part of my co-pending per square inch gauge and at temperatures of of substantially anhydrous hydrogen fluoride containing a minor proportion of dissolved di-. chloromonofluoromethane and a layer comprising dichloromonofluoromethane and separating the layers.

3. The process of separating valuable components from a reaction mixture comprising HCl, HF, CHClFz and CHC12F,0f the character of that obtained by the reaction of HF on CHCla,

which comprises the steps of subjecting the re-- action mixture to anhydrous fractional distillation under pressures of from'about 40-to about 200 pounds per square inch gauge and at temperatures' of from about ---63 C. to about 20 C., adjusted to the pressures to distill off the HCl as substantially pure anhydrous hydrogen chloride, then subjecting the remaining mixture to a further anhydrous fractional distillation under pressures of from aboutO to about pounds per square inch gauge and at temperatures of from about 43-C. to about 20 C., adjusted to the pressures to distill off a mixture comprisingsubstantially the monochlorodifluoromethane and part of the hydrogen fluoride.

4. The process of separating valuable components from a reaction mixture comprising I- IC 1,

HF, CHClFz and CHClzF, of the character of that obtained by'the reaction of HF on CHCla, which comprises the steps of subjecting the reaction mixture to anhydrous fractional distillation under pressures of about 100 pounds per square inch gauge and at about 50 C. to about -40 C. to distill off the H01 as substantially pure anhydrous hydrogen chloride, then subjecting the remaining mixture to a further anhydrous fractional distillation under pressures of about 50 pounds per square inch gauge and at about '5 C. to about 0 C. to distill off a mixture comprising substantially the monochlorodifluoromethane and part of the hydrogen fluoride. 5. The process of separating valuable components from a reaction mixture comprising HCl,

. 7 HF, CHClFz, CHClzF and CHCls, of the character HCI as substantially pure anhydrous hydrogen,

chloride, then subjecting the remaining mixture to a further anhydrous fractional distillation under pressures of from about to about 100 pounds per square inch gauge and at temperatures of from about -43 C. to about 20 (3., adjusted to the pressures to distill ofl a mixture comprising substantially the monochlorodifluoromethane and about 60% of the hydrogen fluoride,

settling the undlstilled mixture until it forms a layer of substantially anhydrous hydrogen fluoride containing a minor proportion of dissolved dichloromonofiuoromethane and a layer of a mixture of dichloromonofluoromethane and chloroform containing a small proportion of dissolved HF, separating the layers, and then subjecting the mixture of dichloromonoiiuoromethane, chloroform anddissolved HP to an anhydrous fractional distillation to separate the dichloromonofluoromethane and HF from the chloroform.

6. The process of separating valuable components from a reaction mixture comprising 301,

HF, CHClFs, CHClzF and CHCla, of the character of that obtained by the reaction of HF on CHCla.

, which comprises the steps of subjecting the reaction mixture to anhydrous fractional distillation under pressures of about 100 pounds per square inch gauge and at about 50 C. to about 40 C. to distill oil the HCl as substantially pure anhydrous hydrogen chloride, then subjecting the remaining mixture to a further anhydrous fractional distillation under pressures, of about pounds per square inch gauge and at about 5 C. to about 0 C. to distill 01! a mixture comprising substantially the monochlorodiiiuoromethane and about ofthe hydrogen fluoride, separating the HF from the monochlorodifluoromethane, settling the undistilled mixture until it forms a layer of substantially anhydrous hydrogen fluoride containing a minor proportion of dissolved dichloromonofluoromethane and a layer of a mixture of dichloromonofluoromethane and chloroform containing a small proportion of dissolved HF, separating the layers, and then subjecting the mixture of dichloromonofluoromethane, chloroform and dissolved HF to an anhydrous fractional distillation to separate the dichloromonofluoromethane and HE from the chloroform.

ANTHONY F. BENNING.

No references cited. 

